Colloids and Surfaces A: Physicochem. Eng.

Aspects 251 (2004) 183–190

Lead sorption from aqueous solutions on chitosan nanoparticles

Lifeng Qi∗ , Zirong Xu
Key Laboratory for Molecular Animal Nutrition of Ministry of Education, Feed Animal Sciences Institute, Zhejiang University,
Hangzhou 310029, PR China

Received 13 October 2003; accepted 7 October 2004

Abstract

Chitosan nanoparticles with different mean size ranging from 40 to 100 nm, which are well dispersed and stable in aqueous solution,
have been prepared by ionic gelation of chitosan and tripolyphosphate (CS-TPP). The physicochemical properties of nanoparticles were
characterized by size and zeta-potential analyzer, atomic force microscopy, FTIR spectra, and X-ray powder diffraction. Its sorption capacity
and sorption isotherms for lead ions were studied. Factors such as initial concentration of lead ions, sorbent amount, temperature, sorbent size,
agitation period, and pH value of solution that influence sorption capacity were investigated. It is found that chitosan nanoparticles could sorb
lead ions effectively, the sorption rate was affected significantly by initial concentrations of solutions, sorbent amount, size, agitation speed,
and pH value of solution. The maximum capacity of lead sorption deduced from the use of Langmuir isotherm equation was 398 mg/g. The
experimental data of lead ions sorption equilibrium correlated well with the Langmuir isotherm equation. New sorption sites were provided by
introducing phosphoric groups, and the freeze-drying procedure led to the low crystallinity of chitosan nanoparticles; as a result, the sorption
capacity was improved greatly.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Chitosan; Nanoparticles; Lead ions; Sorption kinetics; Sorption isotherms

1. Introduction equilibrium. Sorption capacity can be controlled by sorbent

Biopolymers, chitosan is the deacetylated form of chitin
and composed of glucosamine, known as (1–4)-2-amino-2-
deoxy-␤-d-glucose. Chitosan has three types of reactive func-
tional groups, an amino group as well as both primary and
secondary hydroxyl groups at the C-2, C-3 and C-6 posi-
tions, respectively [1]. This special structure makes it ex-
hibit chelation with various metal ions [2]. Muzzarelli [3]
pointed out that chitosan combines with metal ions by three
forms: ion exchange, sorption and chelation. Chitosan has
been broadly used for the sorption of heavy metal ions [4–6].
Further physical and chemical modifications of chitosan have
been made to improve the selectivities and the capacities for
metals ions [7–10]. Chitosan is also characterized by weak
diffusion properties: long contact times are required to reach
∗ Corresponding author. Tel.: +86 571 86971075; fax: +86 571 86091820.
E-mail address: lfqi@zju.edu.cn (L. Qi).
particle size [8]. Due to the low porosity of chitosan, sorp-
tion performances are frequently controlled by mass transfer
resistance. To reduce this resistance to mass transfer, chi-
tosan gel beads have been developed to expand the polymer
structure and reduce its crystallinity favouring sorption rate
[11–13]. However, these treatments results in either a de-
crease of the number of available sorption sites (cross-linking
treatment), or the volumetric sorption capacity (the percent-
age of water in the gel beads can reach 95%) [14]. Controlled
drying can increase the volumetric sorption capacity [15].
Another possibility for increasing this volumetric sorption
capacity is the grafting of supplementary functional groups
[16].
A number of nanoscale inorganic particles (NIPs) offer
favourable properties in regard to selective removal of target
contaminants. For example, hydrated Fe(III) oxides particles
can selectively sorb dissolved heavy metals like zinc, cop-
per or metalloids like arsenic oxyacids or oxyanions [17].

0927-7757/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.10.010
184 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190
Amorphous and crystalline Fe(III) hydroxides have long been
known to possess selective sorption properties toward arsen-
ites and arsenates [18]. Polymer supported nanoparticles have
been prepared and used for selective removal of target arsenic
compounds and heavy metals [17]. Chitosan nanoparticles
had been synthesized based on polymer and applied as drug
carriers as reported in previous studies [19–21].
However, researches about the sorption properties of chi-
tosan nanoparticles are seldom reported now. The unique
character of nanoparticles for their small size, great surface
area and quantum size effect could make it exhibit higher
capacities for metal ions. The present work aims to synthe-
size chitosan nanoparticles by ionic gelation of chitosan and
tripolyphosphate and evaluates their sorption capacity of lead
ions. Freeze-drying was applied in preparation of chitosan
nanoparticles, and new sorption sites polyphosphoric groups
were introduced by slightly crosslinking with tripolyphos-
phate to increase the volumetric density of sorption sites and
the sorption capacity.
2. Experimental
2.1. Materials
Chitosan, obtained from Chitosan Company of Panan city
of Zhejiang province in China, was refined twice by dis-
solving it in dilute acetic acid solution, filtered, precipitated
with aqueous sodium hydroxide, and finally dried in vac-
uum at room temperature [22]. The degree of deacetylation
was about 85%, and weight of chitosan was 220 kDa, de-
termined by viscometric methods [23]. Sodium tripolyphos-
phate (TPP) was supplied by Sigma Chemical Co. (USA).
Lead nitrate was purchased from Shanghai Chemical of China
Medicine Company. All other chemicals were reagent grade.
2.2. Preparation of chitosan nanoparticles
Chitosan nanoparticles have been prepared by our previ-
ous study [24], briefly, chitosan was dissolved at 0.5% (w/v)
with 1% (v/v) acetic acid and then raised to pH 4.6 ∼ 4.8 with
10 N sodium hydroxide. Chitosan nanoparticles formed spon-
taneously upon addition of 1 mL of an aqueous TPP solution
0.25% (w/v) to 3 mL chitosan solution under magnetic stir-
ring. Different mean size of nanoparticles were obtained by
adjusting the ratio of chitosan to tripolyphosphate. Nanopar-
ticles were purified by centrifugation at 9000 × g for 30 min.
Supernatants were discarded and chitosan nanoparticles were
extensively rinsed with distilled water to remove any NaOH
residus, and frozen dried before further use or analysis.
2.3. Morphology and structure characterization of
chitosan nanoparticles
Particle size distribution of chitosan nanoparticles were
determined using Zetasizer Nano-ZS90 (Malvern Instru-
ments). The analysis was performed at a scattering angle
of 90◦ at a temperature of 25 ◦ C using samples diluted to
different intensity concentration with de-ionized distilled
water.
Chitosan nanoparticles were gold coated using a Hitachi
coating unit IB-2 coater under a high vacuum, 0.1 Torr, high
voltage, 1.2 kV and 50 mA. Coated samples were examined
using a XL30-ESEM environmental scanning electron mi-
croscope to characterize the morphology of nanoparticles.
AFM was used for visualization of chitosan nanoparticles
after sorbing lead ions deposited on silicon substrates oper-
ating in contact mode. AFM imaging was performed using
Si3 N4 probes with spring constant 0.06 N/m. FTIR of chi-
tosan nanoparticles were taken with KBr pellets on Nicolet
Nexus 670 Spectrum one FTIR. The X-ray powder diffraction
pattern of chitosan and chitosan nanoparticles were obtained
by a D/max-rA diffractometer.
2.4. Sorption kinetics experiments
Batch experiments for determination of kinetics of lead
ions on chitosan nanoparticles were carried out using a con-
tinuously stirred glass vessel. Different amounts (20, 30 or
50 mg) of accurately weighted powder chitosan nanoparticles
with different mean particles size (40, 70 or 100 nm) were
brought in contact with 50 mL of lead ions solutions under
continuous stirring (speed of agitation 60, 260 or 340 rpm),
at room temperature (25 ◦ C), 50, 75, and 100 ◦ C. The pH
was 5.5. The initial concentration of lead ions was varied to
investigate their effect on the sorption kinetics. During the
kinetic experiments, samples were withdrawn at fixed time
intervals, filtered, and quantified by Flame atomic absorption
spectrophotometer using an AA-6501 model.
2.5. Equilibrium experiments
Batch equilibrium experiments were carried out using chi-
tosan nanoparticles as sorbent. A series of flasks containing
lead nitrate solutions of varying concentrations prepared from
lead nitrate and a fixed mass of chitosan nanoparticles (1 g/L)
were agitated in a rotary shaker at 260 rpm at room tempera-
ture for 24 h. Lead ions uptake experiments were conducted
under constant pH value between 3 and 7 by adding muri-
atic acid or sodium hydroxide as required. After equilibra-
tion, the lead nitrate solutions were filtered through papers
and analyzed. Lead-free and sorbent-free blanks were used
as controls. Amounts of lead ions taken up by the sorbent in
each flask were determined by the following mass balance
equation:
V (C0 − Ce )
Q=
W
where Q is the sorption capacity (mg/g), C0 and Ce are, re-
spectively, the initial and solution phase lead ions concentra-
tion at equilibrium (mg/L), V the solution volume (L), and W
the mass of sorbent (g).
 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190
Fig. 1. Size distribution by volume of chitosan nanoparticles with mean size
about 40 nm.
Fig. 2. Size distribution by volume of chitosan nanoparticles with mean size
about 70 nm.
3. Results and discussion
3.1. Characterization of chitosan nanoparticles
3.1.1. Size and morphology of chitosan nanoparticles
The preparation of chitosan nanoparticles was based on
an ionic gelation interaction between positively-charged chi-
tosan and negatively-charged tripolyphosphate at room tem-
perature [25,26]. The chitosan nanoparticles prepared in the
experiment exhibit white powder shape, and were insoluble
in water, dilute acid, and alkalescent solution.
The mean size and size distribution of each batch of
nanoparticles suspension was analyzed using the Zetasizer
analysis. The size distribution profile, as shown in Figs. 1–3,
represents three typical batches of nanoparticles with differ-
Fig. 4. ESEM analysis of chitosan nanoparticles: (a) ×20,000; (b) ×60,000.
185
Fig. 3. Size distribution by volume of chitosan nanoparticles with mean size
about 100 nm.
ent mean diameter ranging from 40 to 100 nm and a narrow
size distribution (polydispersity index < 1).
The surface morphology of chitosan nanoparticles char-
acterized by ESEM indicate a microporous structure which
favours the sorption for lead ions, and it exhibits aggregates
composed of adjacent nanoparticles as shown in Fig. 4.
Different assemblage shape of chitosan nanoparticles
was obtained under pH 4.0 by AFM observation shown
in Fig. 5(a), the differences on morphology determined by
ESEM and AFM are due to the different preparation pro-
cess of nanoparticles samples. ESEM deals with nanoparti-
cles aggregates powder, while AFM observation was con-
ducted against nanoparticles suspension. After sorbing lead
ions, chitosan nanoparticles can be surrounded by lead ions
as shown in Fig. 5(b). Chitosan nanoparticles can be dis-
persed well in aqueous or acid solution medium and seldom
congregate.
3.1.2. Surface functional groups of chitosan
nanoparticles
The sorption capacity of chitosan can be improved by
the substitution of various functional groups, such as amino
acid esters, oxo-2-glutaric acid and pyridyl [27–29]. Sev-
eral phosphorus derivatives of chitosan have also been syn-
thesized by grafting phosphate or phosphonic acid [30–32].
Tripolyphosphate has also been selected as a possible cross-
linking agent for the preparation of chitosan gel beads
by the coagulation/neutralization effect. Spherical chitosan-
tripolyphosphate chelating beads had been prepared and ap-
186 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190
Fig. 5. AFM photographs of chitosan nanoparticles. (a) before; (b) after sorption of lead ions.
plied in the field of metal ions adsorption due to the enhanced
intraparticular diffusion and excellent uptake capacity [33].
In this work, in order to increase the sorption capacity of chi-
tosan, chitosan nanoparticles were prepared by ionic gelation
of chitosan and tripolyphosphate.
FTIR spectra of chitosan and chitosan nanoparticles have
been analyzed by our previous study, and results showed that
the CONH2 and NH2 groups of chitosan are both slightly
crosslinked with a sodium polyphosphate molecule (Fig. 6)
[24]. Lead-sorbed nanoparticles were formed by sorption
of lead ions. As can be seen from the IR spectrum of chi-
tosan nanoparticles, the peak indicating P O stretching at
1217 cm−1 appear [33], but disappear for the nanoparticles
Fig. 6. Infrared spectra. (a) chitosan; (b) chitosan nanoparticles; (c) lead-
sorbed chitosan nanoparticles.
after sorbing lead ions due to the ionic crosslinking between
lead ions and phosphoric groups. The peaks at 1657 cm−1
(CONH2 ) and 1598 cm−1 (NH2 ) in the spectrum of lead-
sorbed nanoparticles turn sharper and separately shift to 1631
and 1536 cm−1 shown in Fig. 6. This behaviour reflects the
interaction between the amino groups and the metal ions.
Therefore, chitosan nanoparticles provide more sorption sites
for lead ions except the amino and hydroxyl groups by intro-
ducing phosphoric groups due to the slight crosslinking with
tripolyphosphate.
3.1.3. Crystallinity of chitosan nanoparticles
Fig. 7 shows the XRD patterns of chitosan and chitosan
nanoparticles. There are two strong peaks in the diffractogram
of chitosan at 2θ at 10.4◦ and 21.8◦ , their crystal lattice con-
stant ␣ corresponding to 8.470 and 4.075. The peak at 2θ
about 22◦ is attributed to the allomorphic tendon form of
chitosan, which resulted in a strong decrease in sorption ca-
pacities [16,34]. However, no peak is found in the diffrac-
tograms of chitosan nanoparticles. This indicates that the
Fig. 7. X-ray powder diffraction patterns of chitosan and chitosan nanopar-
ticles.
 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190 187

Fig. 8. Kinetics of Pb2+ uptake by chitosan nanoparticles at 25 ◦ C (pH, 5.5). Fig. 9. Influence of nanoparticles amount on lead sorption (mean size,
40 nm; T, 25 ◦ C; initial concentration of lead ions, 100 mg/L; pH 5.5).
crystal structure of the amorphous chitosan has been de-
stroyed after crosslinked with sodium polyphosphate. The
crystallinity of chitosan polymer could play a restrictive role
on metal sorption capacity. Piron and Domard studied the fix-
ation capacities of uranyl ions at saturation for three chitosans
of different crystallinity, and confirmed that a chitosan sample
with low crystallinity allowed rapid sorption kinetics and a
maximum fixation capacity [35]. The crystallinity parameter
of chitosan is a key-parameter in the accessibility to internal
sites for both water and metal ions. Many studies have shown
that decreasing the crystallinity results in an improvement in Fig. 10. Influence of temperature on lead sorption by chitosan nanoparticles
metal ion sorption properties [36]. Several studies have shown (sorbent dosage: 20 mg; mean size, 40 nm; initial concentration of lead ions,
that the type of drying procedure can affect the crystallinity 100 mg/L; pH 5.5).
of polymer [37]. Piron et al. observed that the freeze-drying
procedure limited the crystallinity and produced a structure 3.2.3. Influence of temperature
with wide openings, as a consequence metal sorption kinetics Fig. 10 shows the sorption kinetics obtained at differing
were speeded up [38]. Chitosan nanoparticles exhibit lower temperatures with chitosan nanoparticles. The residual lead
crystallinity due to the freeze-drying procedure, as a result, ion concentration slightly increased with the increase of tem-
the lead sorption rate was improved significantly. perature from 25 to 55 ◦ C. The sorption was faster at 25 ◦ C
than at 40 and 55 ◦ C. Previous studies had shown the little
3.2. Sorption kinetics for lead ions differences for usual temperatures (in the range 5–55 ◦ C) for
copper, zinc or mercury sorption [39].
3.2.1. Influence of initial concentration
The different initial concentration of lead ions solution 3.2.4. Influence of mean size
have an effect on the sorption kinetics illustrated in Fig. 8. In Fig. 11, it could be seen higher sorption capacity when
Higher the initial concentration of lead ions, it would take the mean size of chitosan nanoparticles decreases. Chitosan
more time to reach equilibrium and had lower sorption per- nanoparticles with mean size 40 nm have a high sorption ca-
centage. Lead ions in solution are adsorbed fast with more pacity for 98 mg/g when contacting with 100 ␮g/mL lead
than 50% in 10 min. When the initial concentration of lead ions solution. Increasing the size of the nanoparticles also
ions was 35 mg/L, the sorption percentage reached 81.6% at increased the time required to reach equilibrium. The con-
10 min, the sorption amount was 28.2 mg/g, and the equilib- tact surface of little size nanoparticles can explain the dif-
rium time was just 20 min. When the initial concentration of ferences among various mean sizes of nanoparticles for lead
lead ions increased to 98 mg/L, the sorption percentage was
58% at 10 min, the sorption amount was 56.5 mg/g. The sorp-
tion reached equilibrium after 60 min, the sorption amount
got to 94.5 mg/g, and the sorption percentage increased to
96%. Chitosan nanoparticles can sorb lead ions quickly, and
exhibit a high sorption capacity.

3.2.2. Influence of the nanoparticles amount

The increase of nanoparticles amount increased the
amount of lead sorbed by chitosan nanoparticles. Fig. 9 shows
the results obtained for 20, 30 and 50 mg of chitosan nanopar-
ticles (mean size 40 nm) in contact with 50 mL of lead ion
solution.
Fig. 11. Influence of mean size of nanoparticles on lead sorption (sorbent
dosage: 20 mg; T: 25 ◦ C; initial concentration of lead ions, 100 mg/L; pH
5.5).
188 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190
Fig. 12. Influence of agitation speed on lead sorption kinetics using chitosan
nanoparticles (sorbent dosage: 20 mg; T: 25 ◦ C; mean size: 40 nm; initial
concentration of lead ions, 100 mg/L; pH 5.5).
sorption. The sorption performance for chitosan and deriva-
tives can be affected significantly by the particle size and the
conditioning of the sorbent due to the diffusion restrictions
caused by the low porosity and crystallinity of the raw chi-
tosan [8]. Chitosan nanoparticles can reduce the crystallinity
of the biopolymer and lead to the expansion of the polymer
network so as to increase the accessibility to internal sites
and the sorption rates.
3.2.5. Influence of agitation speed
Fig. 12 shows that the sorption amount of lead increased
significantly with increase of the agitation speed in short con-
tact time, while the sorption capacity showed little difference
at equilibrium. Therefore, the lead sorption capacity was in-
dependent of the agitation speed in the range 60–340 rpm.
Similar results for cadmium sorption on chitosan were ob-
tained by Dzul Erosa et al. [40].
3.3. Influence of pH value on sorption
Fig. 13 shows the effect of pH on the sorption of Pb2+ by
chitosan nanoparticles. It is found that the sorption efficiency
increased with increasing the pH of the solution. Chitosan
nanoparticles chelated lead ions mainly by the amine groups
and tripolyphosphoric groups. Lead ions and protons can bind
with the finite number of amine groups competitively in chi-
tosan, which can make an effect on the sorption [41]. At low
pH value of the solution, the amine and tripolyphosphoric
groups are protonated to varied degrees, reducing the num-
ber of binding sites available for lead ions uptake so that the
extent of lead ions uptake is low in the high concentrations
Fig. 13. Effect of pH on lead ions sorption capacity at equilibrium on chi-
tosan nanoparticles.
of protons. Moreover, the protonation of amine and phospho-
ric groups induced an electrostatic repulsion of lead cations.
When the pH of the solution increased, the competitor effect
decreased as well as the electrostatic repulsion. It is reported
that the pKa value of chitosan is about 6.5 [42], at higher
pH beyond 6.5, precipitation of lead hydroxide occurs simul-
taneously with the sorption of lead ions, which will affect
the sorption of chitosan nanoparticles. Similar results were
shown using chitosan gel beads for the influence of pH on
metal sorption [40]. The pH has also a critical effect on the
distribution and the charge of metal species in solution and
therefore their affinity for the sorbent [16]. The activating
species of lead at mildly acidic pH was Pb2+ and in mildly
alkaline pH it was Pb(OH)2 . Pb2+ is the predominant species
in solution at pH 5.5 [43], while the first hydrolysis product,
Pb(OH)2 is more easily sorbed onto sorbent surfaces, even
at relatively low pH [44]. Involvement of this species could
facilitate the attachment of lead to the surface via oxygen to
form Pb–O bonds [45].
3.4. Sorption isotherms
The most important model of monolayer adsorption came
from the work of Langmuir [46]. The Langmuir adsorption
isotherm assumes that the adsorption can only occur at a
fixed number of definite localized sites, each site can hold
only one adsorbate molecule (monolayer), and the sites are
homogeneous.
Fig. 14 shows the experimental equilibrium isotherms for
sorption of lead ions on chitosan nanoparticles. The experi-
ment showed that the concentration of lead ions remaining in
solution and the sorption capacity increased with the initial
concentration of lead ions increasing. When the concentra-
tion of lead ions at equilibrium was 550.2 mg/L, the sorp-
tion capacity reached 327.5 mg/g, which had been improved
considerably than that of chitosan. Ng et al. reported that the
maximum monolayer capacity for lead with chitosan was just
0.558 mmol/g equal to 99.3 mg/g [47].
Their sorption behaviours can be described with the Lang-
muir adsorption equation [48] as:
Ce Ce 1
= + b
Q Qmax Qmax
where Ce is the equilibrium concentration of lead ions
(mg/L), Q the amount of lead ions sorbed per unit weight of
Fig. 14. Pb2+ sorption isotherm by chitosan nanoparticles at 25 ◦ C and pH
5.5.
 L. Qi, Z. Xu / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 183–190 189

The morphology changes of nanoparticles after sorption of

lead ions are revealed by AFM observations. FTIR spectra re-
veal the functional groups of chitosan nanoparticles and the
interaction with lead ion, the amine and phosphoric groups
of nanoparticles provide sorption sites for lead ions. Chi-
tosan nanoparticles possess lower crystallinity than chitosan
illuminated by XRD patters. The new functional groups and
low crystallinity of chitosan nanoparticles are responsible for
its sorption efficiency. The experiments show that chitosan
Fig. 15. Langmuir plots for Pb2+ uptake by chitosan nanoparticles at 25 ◦ C nanoparticles can sorb lead ions from aqueous solution effec-
and pH 5.5.
tively, and the sorption capacity has been improved greatly
with a maximum sorption capacity of about 398 mg/g. The
Table 1
Effect of separation factor on isotherm shape [9]
experimental data of the sorption equilibrium from lead ions
solution correlate well with the Langmuir isotherm equation.
RL value Type of isotherm
The high sorption capacity of chitosan nanoparticles for lead
RL > 1 Unfavourable ions indicates a promising sorbent for the removal of heavy
RL = 1 Linear
0 < RL < 1 Favourable
metals in polluted water.
RL = 0 Irreversible

Table 2
RL values based on the Langmuir equation
C0 (mg/L) RL values
60 0.665
200 0.373
300 0.284
600 0.166
900 0.117
where C0 stands for the initial concentration of lead ions in solution.
chitosan nanoparticles/chitosan at equilibrium (mg/g), Qmax
the maximum sorption at monolayer coverage (mg/g) and b
the Langmuir sorption equilibrium constant (mL/mg) and it
is a measure of the energy of sorption.
A linearized plot of Ce /Q versus Ce (Fig. 15) gives
Qmax and b, the results obtained are: Qmax = 398 mg/g and
b = 0.0084 (mL/mg). The equation is Ce /Q = 0.0025Ce +
0.2882. The plots demonstrate that the Langmuir equation
provides a reasonable description of the experimental data.
A dimensionless constant separation factor or equilibrium pa-
rameter, RL can exhibit the features of a Langmuir isotherm.
It is defined by [49]:
1 [11] E. Guibal, C. Milot, J.M. Tobin, Ind. Eng. Chem. Res. 37 (1998)
RL =
1 + bC0
where C0 is the initial lead ions concentration (mg/L), and b
the Langmuir sorption equilibrium constant (mL/mg). This
parameter indicates the isotherm shape according to Table 1.
The values of RL calculated for different initial concentrations
for chitosan nanoparticles are given in Table 2. They show
that the sorption of lead ions is favourable.
4. Conclusion
Different mean size of chitosan nanoparticles have been
prepared by ions gelation of chitosan and tripolyphospahte.
Acknowledgements
We would like to thank Zhejiang Provincial Science and
Technology Committee of China (No. 021102680) for finan-
cial support.
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